CN113880974B - 一种基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液及其制备方法及应用 - Google Patents
一种基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液及其制备方法及应用 Download PDFInfo
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Abstract
一种基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液及其制备方法及应用,属于光固化技术领域,光引发剂的结构如下所示,是四芳基取代的吡咯[3,2‑b]并吡咯化合物,R1为吡咯环氮原子所相连的苯基上的取代基,R2为吡咯环碳原子所相连的苯基上的取代基,丙烯酸酯树脂单体为含有C=C不饱和键的酯类,R1为甲基、甲氧基或氢原子;R2为硝基。有益效果是:1、光引发剂对不同波长具有不同的灵敏性;2、采用紫外光固化,而非传统的热固化;3、得到的固化液通过环境友好的LED紫外光光源可以实现辐照固化,避免了紫外光固化施工中涂布后必须立即辐照的问题,可以实现涂布和辐照的分布操作,有利于实现辐照固化获得类似水性涂料的施工方式。
Description
技术领域
本发明属于光固化技术领域,特别涉及一种室温无需避光使用的基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液的制备及应用。
背景技术
光聚合技术,是一种在温和条件下光聚合体系中的光引发剂被光激发,生成承担着引发单体聚合作用的活性物种,使体系由液态快速变为固态的低成本绿色技术。光聚合体系通常由光引发剂、低聚物、单体和负责满足材料特殊使用要求的助剂构成。光聚合技术具有广泛的应用领域,如印刷油墨和不同种类的涂料。最近,通过更先进的技术,如牙科固化或基于光刻的陶瓷制造,其范围进一步扩大。
光引发剂是光固化体系的重要组成部分,可以分为三类:裂解型引发剂、光敏型引发剂、阳离子光引发剂。理想的光引发剂应具廉价,合成简单;光引发剂及其光裂解产物应无毒无味;稳定性好,便于长时间储存;较高的引发效率等优点。在不同的光固化体系中,要选用活性适当的光引发剂,保证用量小,无污染,廉价易得。
大面积施工中,必然会接触日光,日光引起光固化液产生白色凝胶,十分影响施工过程。大面积光源成本高,难制作,未来如果使用辐射固化涂料必须解决光固化液大面积施工的方法,需要室温下无需避光可以稳定不变质的光固化液。目前,这也是辐射固化涂料在建筑涂料等大面积涂装中未得到如水性涂料广泛开发的制约因素。辐射固化液态涂料如果稳定不避光稳定存在,不带来水性涂料在溶剂污染及和UV光固化粉末涂料需要热敏基材和升温加热熔融的问题。
发明内容
本发明的首要目的在于提供一种室温无需避光使用的基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液,所述的基于吡咯并吡咯结构的光引发剂的结构如下所示,是四芳基取代的吡咯[3,2-b]并吡咯化合物,R1为吡咯环氮原子所相连的苯基上的取代基,R2为吡咯环碳原子所相连的苯基上的取代基。所述的丙烯酸酯树脂单体为含有C=C不饱和键的酯类。
R1为甲基、甲氧基和氢原子等;R2为硝基。
所述的光固化液的制备方法主要包括两种:第一种制备方法为先将丙烯酸酯树脂、吡咯并吡咯光引发剂避光条件下按照一定比例混合,搅拌均匀。继续搅拌,正上方使用照射波长为470nmLED照射头照射,直至该混合物的颜色不再变化,停止搅拌,得到所述的光固化液。第二种制备方法为将三羟甲基丙烷三丙烯酸酯、吡咯并吡咯引发剂还可以与双氧水按照一定比例混合,搅拌均匀。继续搅拌,正上方使用照射波长为470nmLED照射头照射,光固化液可以变至无色,其中双氧水取树脂质量分数的0.1%~4%,得到无色的光固化液。
所述的光固化液经过第一种制备方法或第二种制备方法后均无需避光,能够在日光下稳定不发生凝胶。其可以通过365nm光源进行辐射固化应用,由辐照前液体交联固化成固体。365nm光源优选环境友好的LED光源,也适用于高压汞灯、中压汞灯、低压汞灯等紫外光源。
进一步的,所述的丙烯酸酯树脂,包括三羟甲基丙烷三丙烯酸酯或聚乙二醇(二醇)二丙烯酸酯。
进一步的,所述的按照一定比例混合,按照丙烯酸酯树脂质量为1,吡咯并吡咯光引发剂的质量分数的范围在0.1%~2%,优选0.2~1%。混合时可以先将吡咯并吡咯光引发剂溶解于少量的二氯甲烷、乙醇、丙酮等有机溶剂中后再加入丙烯酸酯树脂,溶剂占树脂质量的1%~5%,优选2%~3%。
所述的吡咯并吡咯光引发剂在450~480nm之间具有吸收峰,照射波长为470nmLED照射头照射过程仅会使体系褪色,不发生聚合反应。另外,采用照射波长为470nmLED照射头的光源照度范围在30~100mW cm-2,优选50~80mW cm-2。
本发明的优点及有益效果是:
(1)本发明光引发剂对不同波长具有不同的灵敏性,利用470nmLED照射头照射后,固化液无需避光,使用涂布等大面积操作。避免传统紫外光固化中,大面积施工就要制作大面积光源的局限性,而且大面积光源难制作。并且,
(2)本发明采用紫外光固化,而非传统的热固化。通过相比较而言,紫外光固化;固化时间短,效能高,聚合速率快,产率好;节约能源,紫外光固化技术不需要进行长时间的加热,省水省电;环境友好,紫外固化技术的配方中避免采用有机挥发性物质,三废排出量少。
(3)本发明得到的固化液通过环境友好的LED紫外光光源可以实现辐照固化,避免了紫外光固化施工中涂布后必须立即辐照的问题,可以实现涂布和辐照的分布操作,有利于实现辐照固化获得类似水性涂料的施工方式。
附图说明
图1.实施例1化合物PyBH光引发剂的(a)核磁氢谱及(b)碳谱图。
图2.(a)实施例1化合物PyBH光引发剂的吸收光谱、(b)对比例1化合物PyBMe及PyBOMe光引发剂的吸收光谱。
图3.(a)、(b)、(c)化合物PyBH/三羟甲基丙烷三丙烯酸酯经470nmLED照射头辐照后获得的光固化液的光固化应用,利用365nmLED照射头(1.8mWcm-2)辐照凝胶率随照射时间的变化曲线。
图4.化合物PyBH/三羟甲基丙烷三丙烯酸酯经470nmLED照射头辐照后获得的光固化液在日光下随照射时间凝胶率的变化曲线,及商品化光引发剂TPO日光下随照射时间凝胶率的变化曲线。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1:
在本发明的一个优选的技术方案中,R1=H,R2=NO2。以下是化合物PyBH的结构式:
合成路线如下:
在一个干燥的双口瓶中,开动搅拌,之后加入对硝基苯甲醛1.51g,苯胺0.93g,对甲苯磺酸0.19g,加入冰醋酸30ml,油浴反应90℃空气冷凝,反应0.5h后加入2,3-丁二酮0.86g继续反应3.5h。反应结束后,室温冷却析出沉淀,抽滤干燥后用二氯甲烷重结晶,再次抽滤干燥,得到纯净的化合物。
图1是上述PyBH的(a)核磁氢谱和(b)碳谱图。
1H NMR(400MHz,CDCl3)δ8.10(d,J=8.0Hz,4H),7.56-7.47(m,4H),7.45-7.37(m,5H),7.37-7.29(m,5H),6.82(s,2H).
13C NMR(101MHz,DMSO)δ145.47,139.96,139.25,135.26,134.19,130.32,129.61,128.50,128.27,127.84,125.96,125.72,125.18,97.48.
对比例1
以下是化合物PyBMe的结构式:
PyBMe的合成合成路线按实施例操作步骤,将苯胺0.93g替换为对甲基苯胺g,其他操作不变。
对比例2:
以下是化合物PyBOMe的结构式:
PyBOMe的合成合成路线按实施例操作步骤,将苯胺0.93g替换为对甲氧基苯胺g,其他操作不变。
实施例2
配制浓度为5×10-5molL-1PyBH的二氯甲烷溶液,测定该溶液的紫外-可见吸收光谱。如图2(a)所示,PyBH在467有明显吸收峰。
对比例3
将实施例2中PyBH分别替换为PyBMe、PyBOMe,分别测定它们的紫外-可见吸收光谱。如图2(b)所示。PyBMe、PyBOMe分别在434、478有明显吸收峰。
实施例3:
称取1g三羟甲基丙烷三丙烯酸酯放入包有锡箔纸的玻璃瓶中,再称取2mg光引发剂PyBH,搅拌,混合均匀,将液体倒入透光的玻璃瓶中。正上方使用照射波长为470nmLED照射头照射,直至该混合物的颜色不再变化,停止搅拌,得到所述的光固化液。
实施例4:
称取1g聚乙二醇(二醇)二丙烯酸酯放入包有锡箔纸的玻璃瓶中,再称取2mg光引发剂PyBH,搅拌,混合均匀,将液体倒入透光的玻璃瓶中。正上方用光强为77.4mWcm-2照射波长为470nmLED照射头照射,直至该混合物的颜色不再变化,停止搅拌,得到所述的光固化液。实验结果表明,与实施例3中相比,实施例4样品褪色不变后仍具有明显的颜色,而前者几乎退至无色,即不同单体褪色情况不同,以实际观察到不褪色为止。
实施例5:
称取1g三羟甲基丙烷三丙烯酸酯放入包有锡箔纸的玻璃瓶中,再称取2mg光引发剂PyBH,再加入1滴双氧水,搅拌,混合均匀,将液体倒入透光的玻璃瓶中。正上方用光强为77.4mW cm-2照射波长为470nmLED照射头照射,直至该混合物的颜色不再变化,停止搅拌,得到所述的光固化液。继续用365LED照射头照射得到的固化后,固化后有液态变成固态的过程,颜色与光固化液含单体的影响有关。
实施例6:
称取1g聚乙二醇(二醇)二丙烯酸酯放入包有锡箔纸的玻璃瓶中,再称取2mg光引发剂PyBH,再加入1滴双氧水,搅拌,混合均匀,将液体倒入透光的玻璃瓶中。正上方使用照射波长为470nmLED照射头照射,直至该混合物的颜色不再变化,停止搅拌,得到所述的光固化液。继续用365LED照射头照射得到的固化后,固化后有液态变成固态的过程,颜色与光固化液含单体的影响有关。
实施例7:
PyBH与三羟甲基丙烷三丙烯酸酯(TMPTA)经470nmLED照射头照射后得到的光固化液分别按照0.2wt%:1wt%、1.0wt%:1wt%的比例混合,继续用365LED照射头固化后有液态变成固态的过程,利用红外光谱仪监测双键在6170cm-1的特征峰面积变化,测定双键转化率。双键转化率结果如图3(a)所示。当引发剂PyBH质量分数为1.0wt%时凝胶率达到30%以上。
对比例4:
按照实施例7将PyBH替换为PyBMe,测定双键转化率。双键转化率结果如图3(b)所示。当引发剂PyBMe质量分数为0.2wt%是凝胶率达到50%以上。
对比例5:
将实施例7中将PyBH分别替换为PyBOMe,测定双键转化率。双键转化率结果如图3(c)所示。当引发剂PyBOMe质量分数为1.0wt%时,凝胶率达到50%以上。
实施例8:
将PyBH与三羟甲基丙烷三丙烯酸酯(TMPTA)经470nmLED照射头照射后得到的光固化液与商品化光引发剂TPO与三羟甲基丙烷三丙烯酸酯(TMPTA)的液体样品在相同条件下放置在日光下,观察样品的变化,并测定凝胶率,结果如图4所示。含TPO的液体样品及时秒内发生凝胶样品变质,而前者放置一周均没有发生变质凝胶的现象,利于液态常温施工,无需类似UV粉末涂料等需要热敏基材及升温加热熔融,优势突出。
Claims (4)
2.权利要求1所述的基于吡咯并吡咯结构光引发剂和丙烯酸酯树脂的光固化液的制备方法,其特征在于,第一种制备方法为:先将丙烯酸酯树脂、吡咯并吡咯光引发剂避光条件下按照一定比例混合,搅拌均匀,继续搅拌,正上方使用照射波长为470nmLED照射头照射,直至该混合物的颜色不再变化,停止搅拌,得到所述的光固化液;
或第二种制备方法为:将丙烯酸酯树脂、吡咯并吡咯引发剂与双氧水按照一定比例混合,搅拌均匀,继续搅拌,正上方使用照射波长为470nmLED照射头照射,光固化液能够变至无色,其中双氧水取树脂质量分数的0.1%~4%,得到无色的光固化液;
所述的按照一定比例混合是指:按照丙烯酸酯树脂质量为1,吡咯并吡咯光引发剂的质量分数的范围在0.1%~2%,混合时先将吡咯并吡咯光引发剂溶解于少量的二氯甲烷、乙醇或丙酮有机溶剂中后再加入丙烯酸酯树脂,溶剂占树脂质量的1%~5%。
3.根据权利要求2所述的光固化液的制备方法,其特征在于,经过第一种制备方法或第二种制备方法后均无需避光,能够在日光下稳定不发生凝胶,通过365nm光源进行辐射固化应用,由辐照前液体交联固化成固体。
4.根据权利要求2所述的光固化液的制备方法,其特征在于,吡咯并吡咯光引发剂在450~480nm之间具有吸收峰,照射波长为470nmLED照射头照射过程仅会使体系褪色,不发生聚合反应;另外,采用照射波长为470nmLED照射头的光源照度范围在50~80 mW cm-2。
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